Benzothiazole azo phenol compounds and materials dyed therewith



2,865,909 BENZOTHIAZOLE Azo PHENOL COMPOUNDS AND MATERIALS near) THEREWITH James M. Straley and John G. vFisher, Kingsport, Tenn, tassi gnors to Eastman Kodak Company, Rochester, N. Y., a corporation of New .Fersey No Drawing. Application September 24, 1954 Serial No. 458,262

tion to the dyeing ofvarious textile materials. 7 Insofar as dyeing is concerned, the invention is particularly directed to the dyeing of cellulose acetate textile materials with the The non-metallized monoazo compounds of our invention have the formula:

a chlorocresol, alkyl phenol, methyl 3,5-dihydroxybenzoate, Z-nitroresorcinol and 2- chloro-3,5-dimethyl phenol, wherein the term alkyl as used above refers to an alkyl hydrocarbon group having light and gas are obtainable. tained by dyeing the cellulose acetate textile material with the non-metallized dye compounds of the invention Thus,

carboxylic acid ester having two to four carbon atoms in the acid groups thereof. By cellulose alkyl carboxylic iterates Patent t acid esters having two to four carbon atoms in the acid groups thereof, we mean to include, for example, both C Phtented 2 3,

hydrolyzedand unhydrolyzed cellulose acetate, cellulose propronate, cellulose butyrate, cellulose acetate-propiowidely used cellulose alkyl carboxylic acid ester;

The non-m'etallized mon-oazocompounds of our'invention are prepared by diazotizing a 2-aminobenzotliiazole compound having the formula:

of a dihydroxybenzene, a trihydroxybenze'ne, a dihydrox'y toluene, a dihydroxybenzene monoalkyl e'ther, a dihydroxybenzene monobenzyi ether, a

copper, chromium, manganese, iron or vanadium. non-metallized monoazo compounds can be metallized either on or off the fiber. Metallization can be carried out, for example, by treating the non-metallized dye with a solution or dispersion of the metallizing agent. Al-

Illustrative of the metallizing agents that can be employed are the halides, the sulfates, the acetates, the cyanides, and the thiocyanates of nickel, cobalt, chromium, manganese, iron and vanadium as wellasvarious copper compounds. Thus, nickel chloride, nickel bromide, nickel cobaltous acetate, cyanide, cobalt thiocyanate [Co(SCN) cupric chloride, cupric bromide, cupric acetate, cupric lactate, chromium trichloride, chromium tribromide, chromic sulfate, chromic acetate, chromium thiocyanate [Cr(SCN) manganese chloride,

thiocyanate [Fe(SCN) ferric thiocyanate [Fe(SCN) and vanadium tribromide, are illustrative of the metallizing agents that can be employed.

When the metal complex is formed on a cellulose alkyl carboxylic acid ester, such as cellulose acetate fiber the Next to nickel thioc'yanate' the use of cobalt thiocyanate is preferred. p I

2 amino 6 -'methylsulfonylbenzothiazole, 2 amino- 6 ethyl sulfonylbenzothiazole, 2 amino 6 J n;

2 amino 6 ethoxybenzothiazole,

.thiazole, 2 amino thiazole,

ether, catechol mono-n-propyl ether,

benzene 'droxybenzene di-n-propyl ether,

propylsulfonylbenzothiazole, 2 amino 6 n butylsulfonylbenzothiazole, 2 aminobenzothiazole 6 N- methylsulfonamide, 2 aminobenzothiazole 6 N- ethylsulfonamicle, 2 aminobenzothiazole '6 N npropylsulfonamide, 2 aminobenzothiazole 6 N nbutylsulfonamide, 2 amino 6 methoxybenzothiazole, 2-amino-6-npropoxybenzothiazole, 2 amino 6 6 methylbenzothiazole, 2 amino- 6 ethylbenzothiazole, 2 amino 6 n propylbenzothiazole, 2 amino 6 n --'butylbenzothiazole, 2- amino 6 f3 hydroxyethylbenzothiazole, 2 amino- 6 7 hydroxypropylbenzothiazole, 2 amino 6 6- hydroxybutylbenzothiazole, 2 amino 6 acetylaminobenzothiazole, 2 amino 6 n propionylaminobenzothiazole, 2 amino 6 n butyrylaminobenzothiazole, 2 amino 6 thiomethylbenzothiazole, 2 amino 6- thiocyanobenzothiazole, 2 amino 6 cyanobenzo- 2 amino 6 trifluoromethylbenzothiazole, 2 amino 6 chlorobenzothiazole, 2 amino 6- nitrobenzothiazole, 2 amino 4,7 dimethoxybenzothiazole, 2 amino 5,6 dimethoxybenzothiazole, 2- amino 4,7 diethoxybenzothiazole, and 2 amino- 4,6-dimethylbenzothiazole are representative of the 2- aminobenzothiazole compounds used in the preparation of the azo compounds of our invention.

Catechol, resorcinol, 1,3,5-trihydroxybenzene, 1,2,3- trihydroxybenzene, orcinol (2,4-dihydroxy toluene), resorcinol monomethyl ether, resorcinol monoethyl ether, resorcinol mono-n-propyl ether, resorcinol mono-n-butyl ether, catechol monomethyl ether, catechol monoethyl catechol mono-nbutyl ether, hydroquinone monomethyl ether, hydroquinone monoethyl ether, hydroquinene mono-n-propyl ether, hydroquinone mono-n-butyl ether, catechol monobenzyl ether, resorcinol monobenzyl ether, hydroquinone monobenzyl ether, 1,3,5-trihydroxybenzene monomethyl ether, 1,3,5-trihydroxybenzene monoethyl ether, l,3,5-trihydroxybenzene mono-n-propyl ether, 1,3,5-trihydroxymono-n-butyl ether, 1,2,3-trihydroxybenzene monomethyl ether, 1,3,5-trihydroxybenzene dimethyl ether, 1,3,5-trihydroxybenzene diethyl ether, 1,3,5-trihy- 1,3,5-trihydroxybenzene di-n-butyl ether, l,2,3trihydroxybenzene dimethyl ether, 1,2,3-trihydroxybenzene diethyl ether, 1,2,3-trihydroxybenzene di-n-propyl ether, 1,2,3-trihydroxybenzene di-nbutyl ether, resorcinol monoacetate, resorcinol mono-npropionate, resorcinol mono-n-butyrate, hydroquinone monoacetate, hydroquinone mono-n-propionate, hydroquinone mono-n-butyrate, 3- 8-hydroxyethoxyphenol, 4-p-hydroxyethoxyphenol, 2,4-dimethylphenol, 3,4-dirnethylphenol, 2-chloro-4-methylphenol, 4-methoxy-2-methylphenol, 4-methoxy-2-ethylphenol, 4-methoxy-2-tertiarybutylphenol, 4-methoxy-3-methylphenol, 4-methoxy-3- ethylphenol, 4-methoxy-3-tertiarybutylphenol, methyl 3,5- dihydroxybenzoate, 2-nitroresorcinol and 2-chloro-3,5-dimethylphenol, for example, are illustrative of the phenolic compounds used in the preparation of the azo compounds of our invention.

The non-metallized monoazo dye compounds of our invention have varying utility for the dyeing of cellulose alkyl carboxylic acid esters having two to four carbon atoms in the acid groups thereof, nylon, acrylonitrile polymers, such as polyacrylonitrile and acrylonitrile graft polymers, and polyesters, such as polyethylene terephthalate. After application to these materials, usually in the form of textile materials, the dye may be metallized thereon, if desired. The metallized azo compounds of our invention can be applied by ordinary dyeing or printing techniques to nitrogenous textile materials such as wool, silk, nylon and acrylonitrile polymers, for example. Coloration can also be eifected by incorporating the non-metallized or metallized azo compounds into the spinning dope, spinning the fiber as usual and converting the non-metallized azo compounds to their metallized corporated in the spinning n butoxybenzomide, an acrylate,

metallizing agent can be indope, the fiber spun as usual and then dyed with the non-metallized monoazo compounds to form the metal complex on the fiber. The new metallized dyes of our invention are preferably formed by heating the non-metallized azo dye with the metallizing agent in organic solvents, such as, for example, cellulose acetate, cellulose acetate-propionate, acrylonitrile polymers, polyamides, ethylene glycol monomethyl ether and formamide.

Both the non-metallized and metallized monoazo compounds of our invention are dyes for fibers prepared from graft polymers obtained by graft polymerizing acryloniform if desired. Also the trile alone or together with one or more other monoethylenic monomers with a preformed polymer. The preformed polymer can be a homopolymer (a polymer prepared by polymerization of a single monomer) or it can be an interpolymer such as a copolymer (a polymer prepared by the simultaneous polymerization in a smgle reaction mixture of two monomers) or a terpolymer (a polymer prepared by the simultaneous polymerization in a single reaction mixture of three monomers), or the like, and the graft polymers for which the dyes are particullarly useful are those containing at least 5% by weight of combined acrylonitrile grafted to the preformed polymer molecule.

The graft polymers which can be dyed using the nonmetallized and metallized dyes are thus polymers having directed placement of the polymerized monomeric units in the graft polymer molecule as distinguished from the random distribution obtained in interpolymers which are prepared by simultaneous polymerization of all of the monomeric materials in the polymer. The preformed polymer can be either a homopolymer of any of the Well-known polymerizable monomers containing a single --CH=C group and desirably a CH =C group, or an interpolymer of two or more of such monomers; an the grafting can be effected with the preformed homopolymer or interpolymer in the polymerization mixture in which it was formed (i. e. a live polymer) or with the preformed polymer isolated from the polymerization mixture in which it was formed (i. e. a dead polymer).

The preformed polymer desirably is a homopolymer of a vinyl pyridine, an acrylamide, a maleamide, a fumaraa methacrylamide, a methacrylate, an intoconamide, a citraconamide, a fumaramate, an intaconamate, a citraconamate, a maleamate, or a vinyl ester; or an interpolymer of two or more of such monomers with each other or of at least one of such monomers with one or more different monoethylenic monomers characterized by a CH=C group such as styrene, acrylonitrile, substituted styrenes, vinyl or vinylidene chlorides, vinyl ethers, dialkyl maleates, ,alkenyl ketones, dialkyl fumarates, acrylic acid, methacrylic acid,

- substituted acrylonitriles, fumaronitrile, ethylene and the like.

The graft polymerization is effected by polymerizing acrylonitrile or a mixture of acrylonitrile with any other monoethylenic monomer, including any of the monomers enumerated hereinabove, with the preformed live or dead homopolymer or interpolymer whereby the acrylonitrile alone or together with another grafting monomer is com bined with the preformed polymer molecule to give a graft polymer containing from 5 to by weight of combined acrylonitrile.

The new azo compounds of our invention are of particular utility for dyeing fibers prepared from a graft polymer obtained by graft polymerizing acrylonitrile and an acrylamide or methacrylamide with a preformed c0- polymer of acrylonitrile and the same or different acrylamide or methacrylamide.

U. S. Patent 2,620,324, issued December 2, 1952, U. S. Patent 2,649,434, issued August 18, 1953, and U. S. Eatent 2,657,191 issued October 27, 1953, disclose other a typical graft polymers that can he dyed with the new azo compounds of our invention.

The following-examples in which parts are expressed as parts by weight illustrate our invention.

EXAMPLE 1 5.0 parts of propionic-acetic (1 5') acids were added .at C. to a solution of 3.8 parts of sodium nitrite in 47 parts of concentrated sulfuric acid (94%). A solution of 9.1 parts ofv 2,-amino-6-methoxybenzothiazole in 50,parts ofpropionic-acetic (.1 :5) acids was added below 5.. C. tow the sodium nitrite solution and the resulting reaction mixture was stirred for two hours at 5 C. and filtered. Thefiltrate was added at 5 C. to a solution of 6.2 parts of resorcinol monomethyl'ether in 150 parts of propionic-acetic (1 :5) acids. After two hours stirring at room temperature, the reaction mixture was made were obtained as a reddish-brown powder which dyes cellulose acetate reddish-orange shades.

EXAMPLE 2 By the use of 9.75 parts of 2-amino-6-nitrobenzothiazole and 8.2 parts of phloroglucinol dihydrate in Example 1 in place of 2-amino-6-methoxybenzothiazole and resorcinol monomethyl ether, respectively, 11 parts of a dye compound which dyes cellulose acetate orange EXAMPLE 3 EXAMPLE 4 A cellulose acetate fabric dyed with a 3% dyeing of the dye product of Example 1 was padded with a 2% The cellulose acetate fabric was No bleeding was posure on the Fade-Ometer.

The above example was repeated replacing the nickel thiocyanate solution with 2% solutions of cobalt thiccyanate, chromium thiocyanate and ferricthiocyanate.

The results obtained are as follows:

Final Color on Cellulose Ac tate Fabric Metal Thiocyanate.

The :metallized dyeingsthus obtained exhibited the same excellent fastness properties, particularly with respect to laundering, as the metallized dyeing obtained when a 2% aqueous solution of nickel thiocyanate was employed as the metallizing agent.

EXAMPLE 5 A cellulose acetate fabric dyed with a 3% the dye product of Example 2 was treated with a 2% EXAMPLE 6 tion of 6 parts of Cuprofix (a mixture of 'copper sulfate and a low urea-formaldehyde resin) in 200 parts of water and then dried at C. The padded cellulose acetate fabric was then cured at 160 C. for 5 minutes and than scoured at 60 C. with a solution of one part of Calgon (sodium hexa-meta-phosphate) and 1 part of Igepal CA (a polymerized ethylene oxide-alkyl phenol A 3% dyeing was made on a cellulose acetate yarn containing 1% of CrCl (added tov the cellulose acetate which it was scoured at 60 C. with soap and water, rinsed with water and then dried.

EXAMPLE 9 1 130 parts of concentrated sulfuric acid (94%) were added, with stirring, to a suspension of 11.4 parts of 2-amino-6-methyl-sulfonylbenzothiazole in parts of water. The temperature rose to about 90 C. during the addition of the sulfuric acid. The resultin solution was cooled to 10 C(and a solution of 4 parts of sodium which precipitated was recovered by filtration, washed well with cold water and dried. 15.2 parts of a dye cornand which dyes the acrylonitrile grafter polymer specifically described hereinafter were obtained;

EXAMPLE 10 Example 1 was repeated using 6.2 parts of hydroquinone monomethyl ether in place of resorcinol monomethyl ether. The dye compound obtained dyes cellulose acetate orange shades and the acrylom'trile-graft polymer acetate fabric was dyed a deep terials have good fastness to light.

EXAMPLE 11 A cellulose acetate fabric dyed with the dye product of Example 9 was treated with a 2% aqueous solution of nickel thiocyanate in accordance with the procedure described in Example 4. The cellulose blue-green shade approximating that of Caledon Jade Green on cotton. In contrast to the original orange colored cellulose acetate fabric which bled badly in an AATCC wash test at 120 F.

and faded after hours exposure on the Fade0rneter, the green metallized dyeing showed no alteration or bleeding in a standard AATCC wash test at 160 F. using soap and soda ash and showed only a barely perceptible break after 20 hours exposure on the Fade-Ometer.

EXAMPLE 12 V A cellulose acetate fabric dyed with a 3% dyeing of the dye product of Example was treated with a 2% aqueous solution of nickel thiocyanate in accordance with the procedure described in Example 4. A green metallized dyeing having excellent resistance to the action of light and laundering was obtained.

EXAMPLE 13 9.7 parts of 2-amino-6-ethoxybenzothiazole in 50 parts of propionic-acetic (1:5 acids were cooled to 5 C. and added to a solution of nitrosyl sulfuric acid prepared by adding the reaction product of 3.8 parts of sodium nitrite and 46 parts of concentrated sulfuric acid to 50 parts of propionic-acetic (1:5) acids. After stirring the reaction mixture for two hours between 0 C. and 5 C., a solution of 7 parts of resorcinol monomethyl ether in 50 parts of propionic-acetic (1:5) acids was added. After completion of the coupling reaction which takes place, the mineral acid present in the reaction mixture was made neutral to Congo red paper by the addition of ammonium acetate and the reaction mixture was allowed to stand at room temperature. The reaction mixture was then drowned in water and the dye product which precipitated was recovered by filtration, washed well'with water and dried. 14.3 parts of a dye compound which dyes cellulose acetate orange shades and the acrylonitrile graft polymer specifically described hereinafter were obtained. Both dyeings possess good fastness to for two hours .light.

A cellulose acetate fabric dyed with a 3% dyeing of the dye product of Example13 was treated with a 2% aqueous solution of nickel thiocyanate in accordance with the procedure described in Example 4. A deep blue dyeing having excellent fastness to light and washing was obtained.

EXAMPLE 15 Example 9 was repeated using 6.5 parts of 3,4-dimethylphenol in place of hydroquinone monomethyl ether. The dye product obtained dyes cellulose acetate orange shades and the acrylonitrile graft polymer specifically described hereinafter. Both dyeings have good fastness to light.

EXAMPLE 16 A celllulose acetate fabric dyed with a 3% dyeing of the dye product of Example 15 was treated with a 2% nickel thiocyanate in accordance with Example 4. A green metalhaving excellent fastness to light and washing was obtained.

EXAMPLE 17 130 parts of concentrated sulfuric acid (94%) were added, with-stirring, to a suspension of 11.4 parts of 2- amino-G-methylsulfonylbenzothiazole in 120 parts of water. The temperature rose to about 90 C. during the a 3% dyeing of dye compound was addition of the sulfuric acid. The resulting solution was cooled to -l0 C. and a solution of 4 parts of sodium nitrite in parts of concentrated sulfuric acid was added dropwise while maintaining the temperature below -5 C. After two hours at C., the diazonium solution resulting was run into a solution of 7 parts of hydroquinone monomethyl ether in 500 parts of water while keeping the temperature below 5 C. by the addition of ice. After addition of the diazonium solution the reaction mixture was stirred for one hour without cooling and then diluted with an equal volume of water. The dye compound which precipitated was recovered by filtration, washed with cold water until neutral and dried. 16.4 parts of a dye compound identical to that obtained in Example 9 were thus obtained.

EXAMPLE 18 1.82 parts of the dye compound of Example 17 were refluxed in 30 parts of acetone and 4 parts of concentrated ammonium hydroxide were added following which a solution of 1.37 parts of nickel acetate tetrahydrate in 30 parts of acetone were also added. The reaction mixture was refluxed for two hours more and then drowned in 800 parts of water. 'The metallized dye compound which precipitated was recovered by filtration and washed with water until the run off was colorless. The metallized dye compound was dried at 110 C. 2.0 parts of the metallized dye compound were obtained. When incorporated into films, yarns, etc., of cellulose acetate, it imparts thereto deep greenish-blue shades having good fastness properties.

EXAMPLE 19 1.56 parts of the dye product of Example 1 were dissolved in parts of ethyl alcohol and a solution of 5 parts of ammonium thiocyanate and 2 parts of NiCl .6H O in 15 parts of water were added with stirring. The reaction mixture thus obtained was heated at C.- C., with stirring, until no further color change was observed, after which it was drowned in 500 parts of water. The metallized dye compound which precipitated was recovered by filtration, washed well with water and dried. 1.65. parts of the metallized dye compound were thus obtained. Attractive shades of blue are obtained when this metallized dye product is incorporated by known means into plastic objects.

EXAMPLE 20 1.56 parts of the dye compound of Example 10, 2 parts of NiCl .6H O, 2 parts of sodium carbonate and 50 parts of the monomethyl ether of ethylene glycol were heated together at C.- C. for two hours with stirring. The reaction mixture was then drowned in 500 parts of water and the metallized dye product which precipitated was recovered by filtration, washed well with water and dried. The metallized dye compound thus obtained imparts green shades having good fastness to light and laundering when incorporated into a cellulose acetate dope solution which is then spun into yarn.

EXAMPLE 21 1.81 parts of the dye compound of Example 15 were refluxed in 30 parts of acetone and 4 parts of concentrated ammonium hydroxide were added following which a solution of 1.37 parts of nickel acetate tetrahydrate in 30 parts of acetone were also added. The reaction mixhours more and then drowned in 800 parts of water. The metallized dye compound which precipitated was recovered by filtration and washed with water until the run off was colorless. The metallized dried at C. 2.0 parts of the metallized dye compound were obtained. It imparts fast green shades when incorporated by known means into plastic obiects.

EXAMPLE 22v 1.63 parts of thedye compound of Example 13 were refluxed in 30 partso facetone and 4 parts of concentrated ammonium hydroxidevwere added following which asolution of 1.37 parts of nickel acetate tetrahydrate in 30 parts of acetone werealso added. The reaction mixture was refluxed for two hours more and then drowned in 800 parts of water. The metallized dye compound which precipitated was recovered by-fil tration and Washed with water until the run off was colorless. The metallized dye compound was dried at'110-C. 1.7 to 1.8 parts of the metallized dye compound were obtained. It colors films, filaments, etc., of cellulose acetate blue; shades having good fastness properties when incorporated therein by known means.

Thedyocompounds otExamplesl, 2,and..3 colorrthe acrylonitrile graft polymer specifically described hereinafter blue, red and brown shades, respectively.v

The following tabulation furtherillustrates the monoazo compounds of our invention and sets forth the colors e n nrmet l z d ompounds yie d. on. (.1) llulose. acetate and (2) an acrylonitrile graft polymenas, well as the colors obtainedon cellulose acetate when thenonmetallized compounds are metallized on the fiber. The preparation of the acrylonitrile graft polymer referred to in the tabulation is described immediately following the tabulation. C. A. refers to cellulose acetate,. Original, refers to the non-metallized dyeing and Final refers to 2-Aminobenzothlazole Compound Coupling Component the metallized dyeing.

Color on CA Color; on

Ac 1 Metalllzlng nitills I Agent Graft Original Final Polymer Original Unszgbstituted.

1, 2, 3-Trihydroxybenzene do Resoreinol.

-Cl:1loro-4-methy1phen01 0 PhloroglucinoL do ii rc'iiidfj brown violet I do. grey-vi let" dullgiolet.-.

2-Amln0benzothiazole Compound Coupling Component Metalllzlng Agent Original Color on CA Color on Acrylonltrlle Graft Polymer Original 4-Methoxy Hydroquinone monoethyl other...

5,6 lgimethoxyflu 3 4-D1methylphenol o o D o Z-Ohloro-t-methylphenoL originate-11.5mm-

sanitar-amateur:

.do fi-lidlydroxyethoxyphenol.

D Besorcinol monomethyl ether- D o. -do

D o. 2-Ghloro-4-methylphenol D o do G-Methoxyu 2-Oh1or03,S-dimethylphenol D o do Hydgoqulnone monobe yl ethe o Hydroquinone monobutyl ether.-.

Preparation of acrylonitrile graft polymer 3.0 g. of acrylonitrile and 7.0 g. of N-methyl methacrylamide were emulsified in 40 cc. of water containing 0.15 g. of potassium persulfate and 0.01 g. of tertiary dodecyl mercaptan. The emulsion was. heated at 60 C. until 94% or more of the monomers had copolymerized. This result is usually accomplished by heating for about 12 hours. The copolymer contained approximately 30% by weight of acrylonitrile and 70% by weight of N- methyl methacrylamide. The mixture was then cooled to room temperature, 50 cc. of water added and the mixture agitated until a homogeneous solution of dope containing by weight of the copolymer resulted.

30.7 g. (3.07 g. of copolymer) of the above prepared solution or dope of the copolymer were placed in a jacketed reactor provided with an agitator and heat exchanger. There were then added 10 g. of acrylonitrile, 114 c. of water, 0.58 g. of 85% phosphoric acid, 0.1 g. of potassium persulfate, 0.17 g. of potassium metabisulfite, 0.1 g. of tertiary dodecyl mercaptan and 0.56 g. of a solution in water of N-methyl methacrylamide and the mixture heated, with stirring, to allowed to level ofi at 3739 C. After the heat of polymerization had been removed and when the conversion of the acrylonitrile to polymer had reached 96% or more, which is usually accomplished in a period of about 12 hours, the temperature was raised to 90 liquor was removed by centrifuging the polymerization C. and then r C. The mother mixture, the polymer precipitate being reslurried twice 7 with water and centrifuged to a moisture cake. The cake was dried under vacuum at C. in an agitated dryer. The overall yield of modified polyacrylonitrile product was over After hammer-milling, the dry powder, now ready for spinning, was stored in a moistureproof container.

The acrylonitrile graft polymer prepared as above and containing about 18% by weight of N-methyl methacrylamide was soluble in N,N-dimethyltormamide. Fibers spun by extruding a solution of the polymer product in N,N-dimethylformamide into a precipitating bath had a softening temperature, of about 240 C., an extensibility of about 20-30 percent depending on the drafting and relaxing conditions, and showed excellent affinity for dyes.

In order that the preparation of the azo compounds of our invention may be entirely clear, the preparation of certain intermediates used in their manufacture is described hereinafter.

Preparation of 2-amin0-6-methylsulfonylbenzothiazole A solution of 200 parts of bromine in 300 parts of acetic acid was added over the course of about 1 hour to a mixture of 171 parts 202 parts of acid. The temperature was held below 35 addition and after complete addition of the of p-aminophenylmethylsulfone and thiocyanate in 1750 parts of acetic C. during the bromine-acetic sodium acid mixture, the reaction mixture was stirred for 18 hours. The reaction product was recovered on the filter by filtration,

washed with acetic acid and then dispersed in 6000 parts of water. tained was heated to The reaction mixture thus obboiling and then an alkali such as caustic soda or sodium carbonate was added until the pH of the reaction mixture was about 6. The reaction mixture was then cooled, filtered and the reaction product which collected on the filter was and dried at washed well with water C. to parts of 2-amino-6- methylsulfonylbenzothiazole were obtained as light yellow crystals melting at 226 Preparation of 2-acetylaminc-64hiocyanobenzvthiazole To a solution of 18.6 parts of aniline and 30.4 parts of ammonium thiocyanate in 15 C. 14.2 parts of chlorine were 17 C. 30 minutes after parts of sodium acetate thiocyanate were added holding the temperature of 300 parts of acetic acid at bubbled in at 15 C.- addition of the chlorine 15.6

to the reaction mixture. While the reaction mixture below 35 C., 14.2 parts of chlorine were passed in and the reaction mixture was stirred overnight at room temperature. The solid present in the reaction mixture was recovered by filtration, washed with and then suspended in 600 parts of water. thus obtained was heated to parts of sodium acetate 50 parts of acetic acid The mixture boiling and filtered. 30 were added to the filtrate and the solid which precipitated was collected at 70 C. on a filter, washed with 200 parts of cold water and dried at 100 C.

30 parts of a product melting at 187 C.-

188 C. were thus obtained.

30 parts of acetic auhydride were added at 80 C. to

a solution of 52.6 parts of the above product in 81 parts of acetic acid, and the temperature of the reaction mixture was held at 80 C.90 C. for one hour. The reaction mixture was then poured into 1000 parts of cold water and the product which precipitated was recovered by filtration, dried at 60 washed with 500 parts of water and then C. 62 parts of Z-acetylamino-G-thiocyaum and 30.4 parts of ammonium Preparation of 2-amin0-6-ethylsulfonylb enzothiazoie A solution of 26.4 parts of crystalline sodium sulfide and 24.9 parts of 2-acetylamino-6-thiocyanobenzothiazole in 150 parts of ethyl alcohol'were refluxed together for minutes and after cooling the reaction mixture to 20 C., 16.3 parts of ethyl iodide were added at one time and the reaction mixture resulting was refluxed for one hour. The reaction mixture was then poured into 1000 parts of water and the product which precipitated was recovered by filtration, washed well with water and dried at 60 C. 23.6 parts of 2-acetylamino-6-ethylthiobenzo-thiazole melting at 168 C.l69 C. were obtained. If desired, the quality of the product can be checked by hydrolyzing a little of the product with acid to 2-amino G-ethylthiobenzothiazole meltin'gat 137 C.139 C.

19 parts of 30% aqueous hydrogen peroxide were added to a solution of 15.5 parts of 2-acetylamino-6- ethylthiobenzothiazole in 53 parts of acetic acid while maintaining the temperature of the reaction mixture between 80 C.-90 C. The reaction mixture was maintained at'this temperature for one hour and then poured into 500 parts of cold Water. The solid present in the reaction mixture was recovered by filtration and then suspended in a'mixture of 800 parts of water and 100 parts of concentrated hydrochloric acid. The reaction mixture thus obtained was heated to boiling and then filtered. The filtrate was neutralized with sodium acetate, cooled to 25 C. and filtered. The product collected on the filter was washed with cold water and dried at 60 C. 8.5 parts of 2-amino-6-ethylsulfonylbenzothiazole melting at 173 C.175 C. were thus obtained.

Preparation of 2-amin0-o-isopropylsulfonylbenzothiazole This compound was prepared in accordance with the procedure described for the preparation of 2-amino-6- ethylsulfonylbenzothiazole using 17.76 parts of isopropyl iodide in place of ethyl iodide. The melting point of the 2-acety1amino-6-isopropylthiobenzothiazole formed during the process was 174 C.-175 C. while that of the final product Z-amino-6-isopropylsulfonylbenzothiazole was 207 C.209 C.

2-ari1ino-6-n-propylsulfonylbenzothiazole is similarly prepared by the use of 17.76 parts of n-p'ropyl iodide in place of isopropyl iodide in the foregoing example.

Preparation of 2-amin0-6-is0butylsalfony benzothiazole This compound was prepared in accordance with the procedure described for the preparation of 2-amino-6- ethylsulfonylbenzothiazole using 14.3 parts of isobutyl bromide in place of ethyl iodide. The melting point of the 2-acetylamino-6-isobutylthiobenzothiazole obtained was 167 C.-168 C. while that of the final product 2- amino-6-isobutylsulfonylbenzothiazole was 206 C.- 207 C.

2-amino-6-n-butylsulfonylbenzothiazole is similarly prepared by using 14.3 parts of n-butyl bromide in place of isobutyl bromide in the foregoing example.

Preparation of 2-amin0-6-triflu0romethylsulfonylbenzm thiazole 1:4 c t te w thstand. t rins- P duct which formed wasrecoyeredbyv filtration, washed well with cold. water and dried at C. 33 to 70 parts of 2-amino-6 trifluoromethylsulfonylbenzothiazole melting at 206-208 C. were thus obtained.

addition of sodium Preparation of Z-am'inofi-trifluoromethylbenzothiazole 12.5 parts of bromine in 20 parts of acetic acid were added dropwise, with stirring, to a solution of 12.4 parts of p aminobenzotrifiuoride and 12.7 parts of sodium thiocyanate in parts of acetic acid while maintaining the temperatureof the reaction mixture below 35 C. The reaction mixturersulting was stirred for 12 hours following which the solid 'p'resent therein was removed by filtration. The filtrate was poured into 1000 parts-of water and the mineral acid therein was neutralized by the addition of sodium acetate wi'th 'good'agitation'. The product which formed wastecovereagby filtration, washed well with cold water and'dried under vacuuni'at 45 C. 7.710.2 parts of 2-amino 6-trifluoromethylbenzothiazole melting at 1155-1165 C. were thus obtained.

Preparation of 2-amin'0 6-,6-hydroxyethylbenzothiazole 255.7 grams of bromine in400 cc. of acetic acid were added graduallyuoyer a period of '1 hour with goodstirring to a solution "05219.2 grams' of p-aminophenylethyl alcohol and 259.2 grams of sodium thiocyanate in 2400 cc. of acetic while maintaining the temperature of the reaction mixture below 15 C. The reaction mixture resulting was stirrred for 2.hou'rs at 10 C.-12 C. and the product which formed was recovered on the filter by filtration and washed with 300 cc. of acetic acid. The product filter cake thus obtained was dissolvedin 1600 cc. of water at about 40C. and the reaction mixture was made alkaline by the addition of sodium hydroxide. The reaction mixture thus obtained-was heated to boiling and then cooled to 15 C. and filtered. The product obtained on the filter was. washed with water until'neutral and then dried at 100 C. 206 to 230 grams of 2-amino- G-fl-hydroxyethylbenzothiazole were thus obtained in the formof white crystals meltingat C.177 C.

Another alkali metal thiocyanate such as potassium thiocyanate, for example, can be used in place of sodium thiocyanate in the foregoing examples. alkaline agent, such as sodium carbonate, sodium bicarbonate, potassium can be used to neutralize the mineral acid in place of sodium acetate.

The preparation of p-aminophenyltrifluoromethylsulfone is described in British Patent 485,592.

The non-metallized monoazo, dye compounds of our for example, wool, silk, nylon and acrylonitrile polymers, such as polyacrylonitrileand acrylonitrile graft polymers, in the form of an aqueous dispersion and are ordinarily so applied.

To illustrate, the dye compound is finely ground with a dispersing agent such, as sodium, lignin sulfonate, Turkey red oil, soap, or an oleyl glyceryl sulfate and the resulting mixture is dispersed in water. The dye bath thus prepared is heated to a temperature approximating C.-55 to be dyed is immersed in the dyebath, following which the temperature is gradually raised to 80 C.90 C. and maintained at this temperature untilv dyeing is complete, usually onehalf to two hours. From time to, time throughout the dyeing operation, the materialis worked topromoteeven Similarly, another dyeing. Upon completion of the dyeing operation, the textile material is removed from the dye bath, washed with an aqueous soap solution, rinsed well with water and dried. In the case of certain of the acrylonitrile graft polymers described hereinbefore it is necessary to dye at the boil for an extended period of time. Instances may be encountered where the fiber is not satisfactorily colored by the dyeing procedure just described. In these instances special dyeing techniques, such as the use of pressure, for example, developed by the art for the coloration of materials diflicult to color may be employed.

Widely varying amounts of dye can be used in the dyeing operation. The amount of dye used can be, for example, /3 to 3% (by weight) of that of the textile material although lesser or greater amounts of the dye can be employed.

The following example illustrates one satisfactory way in which the fibers of the acrylonitrile graft polymers can be dyed using either the non-metallized or metallized azo compounds of our invention. are ground with an aqueous solution of sodium lignin sulfonate until well dispersed or alternately the dye can be dissolved in 5 cc. of hot ethylene glycol monoethyl ether. The dispersion or solution, as the case may be, is then poured into 150 cc. of water to which a small amount of a surface-active agent such as Igepon T Nekal BX (sodium alkylnaphthalenesulfonate) of Orvus (sodium lauryl sulfate-type) has been added. The dye bath is then brought to the desired temperature and 5 grams of well wet-out fibers of the graft polymer are added thereto. Dyeing is continued until the proper shade is reached. From time to time throughout the dyeing operation, the material is worked to promote even dyeing.

The expression propionic-acetic (1:5) acids refers to a mixture of propionic and acetic acids in which there are five parts by volume of acetic acid to 1 part of volume of propionic acid.

The non-metallized azo compounds dye nylon substantially the same shade as they dye acrylonitrile polymers.

Acrylonitrile graft polymers including those of the type specifically described hereinbefore are described and claimed inCoover U. S. application Serial No. 408,012, filed February 3, 1954, 2 amino 6 trifluoromethylsulfonylbenzothiazole is described and claimed by Straley and Fisher U. S. application Serial No. 413,954, filed March 3, 1954, now abandoned. 2-amino-6-trifiuoromethylbenzothiazole is described and claimed by Straley and Fisher U. S. application Serial No. 413,955, filed March 3, 1954, now abandoned.

We claim:

1. A complex metal compound which contains one of the metals selected from the group consisting of chromium, cobalt, copper, iron, manganese, nickel and vanadium in complex combination with a monoazo compound having the formula:

as used above refers to an alkyl hydrocarbon group hav- 16 milligrams of dye ing 1 to 4 carbon atoms and wherein the radical designated X is devoid of substituents other than those indicated above.

2. Complex nickel compounds of the monoazo compounds having the formula set forth in claim 1.

3. Complex cobalt compounds of the monoazo compounds having the formula set forth in claim 1.

4. A complex metal compound which contains one of the metals selected from the group consisting of chromium, cobalt, copper, iron, manganese, nickel and vanadium in complex combination with a monoazo compound having the formula:

wherein Ar represents an ortho-arylene radical of the benzene series devoid of a sulfonic acid group and X represents the radical of dihydroxybenzene monoalkyl ether, wherein the term alkyl refers to an alkyl hydrocarbon group having I to 4 carbon atoms and wherein said dihydroxybenzene monoalkyl ether radical is devoid of other substituents.

5. A complex metal compound which contains one of the metals selected from the group consisting of chromium, cobalt, copper, iron, manganese, nickel and vanadium in complex combination with a monoazo compound having the formula:

wherein Ar represents an ortho-arylene radical of the benzene series.

6. A monoazo compound having the formula:

s Ar\ wherein Ar represents an ortho-arylene radical of the benzene series devoid of a sulfonic acid group and represents the radical of a phenol selected from the group consisting of dihydroxybenzene, trihydroxybenzene, dihydroxy toluene, dihydroxybenzene monoalkyl ether, dihydroxybenzene monobenzyl ether, trihydroxybenzene monoalkyl ether, trihydroxybenzene dialkyl ether, dihydroxybenzene monoalkylacylate, B-hydroxyethoxypbcnol, dimethyl phenol, chlorocresol, methoxy substituted alkyl phenol, methyl 3,5-dihydroxybenzoate, 2-nitroresorcinol and 2-chloro-3,5-dimethyl phenol, wherein the term alkyl as used above refers to an alkyl hydrocarbon group having 1 to 4 carbon atoms and wherein the radical desi nated X is devoid of substituents other than those indicated above.

7. A monoazo compound having the formula:

Ar CN=NX ortho-arylene radical of the benzene series devoid of a sulfonic acid group and X represents the radical of dihydroxybenzene monoalkyl ether, wherein the term alkyl refers to an alkyl hydrocarbon group having 1 to 4 carbon atoms and wherein said dihydroxybenzene monoalkyl ether radical is devoid of other substituents.

8. A monoazo compound having the formula:

wherein Ar represents an wherein Ar represents an ortho-arylene radical of the benzene series devoid of a sulfonic acid group. 9. The azo compound having the formula:

10. The azo compound having the formula:

OCH:

CHsO

H 11. The azo compound having the formula:

CHzOgS I OH 12. The azo compounds having the formula:

S OH: emote \C N=N 13. The azo compounds having the formula:

14. A complex nickel compound of the azo compound of claim 9.

15. A complex nickel compound of the azo compound Of claim 10.

16. A complex nickel compound of the azo compound of claim 11.

17. A complex nickel compound of the azo compound of claim 12.

18. A complex nickel compound of the azo compound of claim 13.

19. As a composition of matter, the azo compounds selected azo compounds having the formula:

References Cited in the file of this patent UNITED STATES PATENTS 

1. A COMPLEX METAL COMPOUND WHICH CONTAINS ONE OF THE METALS SELECTED FROM THE GROUP CONSISTING OF CHROMIUM, COBALT, COPPER, IRON, MANGANESE, NICKEL AND VANADIUM IN COMPLEX COMBINATION WITH A MONOAZO COMPOUND HAVING THE FORMULA: 